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WO2018079605A1 - Halloysite à surface modifiée, procédé de production d'halloysite à surface modifiée et réaction catalytique - Google Patents

Halloysite à surface modifiée, procédé de production d'halloysite à surface modifiée et réaction catalytique Download PDF

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Publication number
WO2018079605A1
WO2018079605A1 PCT/JP2017/038513 JP2017038513W WO2018079605A1 WO 2018079605 A1 WO2018079605 A1 WO 2018079605A1 JP 2017038513 W JP2017038513 W JP 2017038513W WO 2018079605 A1 WO2018079605 A1 WO 2018079605A1
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halloysite
group
modified
purified
containing group
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Japanese (ja)
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秀文 近内
島津　省吾
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JFE Mineral Co Ltd
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JFE Mineral Co Ltd
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Priority to US16/344,955 priority Critical patent/US11932544B2/en
Priority to CN201780065612.0A priority patent/CN109890755B/zh
Priority to KR1020197011881A priority patent/KR102227904B1/ko
Priority to JP2018547722A priority patent/JP7104630B2/ja
Priority to EP17865368.9A priority patent/EP3533761A4/fr
Publication of WO2018079605A1 publication Critical patent/WO2018079605A1/fr
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
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    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/10—Infrared [IR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Definitions

  • the present invention relates to a surface-modified halloysite, a method for producing a surface-modified halloysite, and a catalytic reaction.
  • Non-Patent Document 1 As a method for hydrolyzing cellulose to synthesize glucose, a method using carbon activated with an alkali as a solid catalyst (Non-Patent Document 1) and a method using sulfonated carbon (Non-Patent Document 2) have been proposed.
  • a method for synthesizing hydroxymethylfurfural (HMF) which is expected as a biofuel and plastic raw material, from fructose, a naturally occurring sugar
  • DMSO dimethyl sulfoxide
  • An object of the present invention is to provide a novel solid catalyst, a method for producing the solid catalyst, and a catalytic reaction using the solid catalyst, which exhibit high catalytic activity as in Non-Patent Documents 1 to 3.
  • the present inventors have found that a halloysite having a carboxy group-containing group or a sulfo group-containing group on the surface exhibits high catalytic activity, and has led to the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a surface-modified halloysite that is a halloysite having a carboxy group-containing group or a sulfo group-containing group on the surface.
  • the surface-modified halloysite according to the above (1) which is a halloysite having a hydroxyl group on the surface.
  • the surface-modified halloysite according to the above (1) or (2) wherein at least a part is a nanotube shape.
  • a method for producing a surface-modified halloysite wherein the surface-modified halloysite according to (1) or (2) is produced by reacting halloysite with a carboxylic acid anhydride or a cyclic sulfonate ester.
  • a method for producing a surface-modified halloysite wherein the surface-modified halloysite according to the above (3) is produced by reacting a halloysite containing a nanotube-shaped halloysite with a carboxylic acid anhydride or a cyclic sulfonic acid ester.
  • the polysaccharide is hydrolyzed to synthesize a monosaccharide, or the fructose is dehydrated to hydroxy.
  • Catalytic reaction according to (6) above which synthesizes methylfurfural.
  • a novel solid catalyst exhibiting high catalytic activity eg, high yield, high selectivity, high reaction conversion, particularly high yield
  • a method for producing the solid catalyst e.g., a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen-sulfate, a hydrogen
  • FIG. 1 shows FT-IR spectra of halloysite before and after surface modification.
  • FIG. 2 represents the XRD pattern of halloysite used in the examples.
  • FIG. 3 represents FT-IR spectra of halloysite before and after surface modification.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the surface modified halloysite of the present invention (hereinafter also referred to as “the halloysite of the present invention” or “surface modified halloysite”) is a halloysite having a carboxy group (—COOH) -containing group or a sulfo group (—SO 3 H) -containing group on the surface. It is.
  • the hyilosite having a carboxy group-containing group on the surface is also referred to as “Hs—COOH”
  • the halloysite having a sulfo group-containing group on the surface is also referred to as “Hs-PS”.
  • the halloysite of the present invention has a structure in which a carboxy group-containing group or a sulfo group-containing group is bonded to the surface of a halloysite having a fine structure (for example, a nanotube shape or the like), the fine structure becomes a reaction field. It is presumed to show high catalytic activity.
  • halloysite is a clay mineral represented by Al 2 Si 2 O 5 (OH) 4 .2H 2 O or Al 2 Si 2 O 5 (OH) 4 .
  • the halloysite may contain nanotube-shaped halloysite (halloysite nanotube).
  • the halloysite nanotubes generally have a submicron sized hollow tubular structure, the outer surface being mainly made of silicate SiO 2 and the inner surface being mainly made of alumina Al 2 O 3 .
  • the halloysite of the present invention is in the form of the above-mentioned nanotubes because the effect of the present invention is more excellent.
  • examples of other shapes include a sheet shape, a spherical shape, an angular nodule shape, and a plate shape.
  • the length of the nanotube is preferably 2 to 1000 nm, and more preferably 2 to 500 nm, because the effect of the present invention is more excellent.
  • the inner diameter of the nanotube is preferably 2 to 200 nm and more preferably 2 to 100 nm for the reason that the effect of the present invention is more excellent.
  • the halloysite of the present invention is preferably composed of a surface-modified halloysite at least partially in the form of a nanotube, and the form of the aggregate may be a powder or a granulated product.
  • a granulating operation may be appropriately added before surface modification or before use as a solid catalyst. Examples of the shape of the granulated product at this time include cylindrical pellets, spheres, granules, and flakes.
  • known methods such as extrusion, rolling, and spray drying can be applied.
  • the position where the halloysite of the present invention has a carboxy group-containing group or a sulfo group-containing group is not particularly limited as long as it is a surface, but when the halloysite of the present invention is in a nanotube shape, the effect of the present invention is more excellent,
  • the inner surface of the nanotube is preferred.
  • the form of bonding of the carboxy group-containing group or the sulfo group-containing group to the surface is not particularly limited, but a covalent bond is preferable because the effect of the present invention is more excellent.
  • the carboxy group-containing group or the sulfo group-containing group does not easily flow out into the solvent during the catalytic reaction (for example, the outflow of the surface modifier described later). Halloysite exhibits higher catalytic activity. This is particularly noticeable when the solvent used for the catalytic reaction is a polar solvent (for example, water, methanol, ethanol).
  • the carboxy group-containing group of the halloysite of the present invention is a carboxy group or a group containing a carboxy group.
  • the carboxy group-containing group is preferably a group represented by -L-COOH because the effect of the present invention is more excellent.
  • L represents a single bond or a divalent organic group.
  • the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted divalent aromatic hydrocarbon group.
  • the sulfo group-containing group of the halloysite of the present invention is a sulfo group or a group containing a sulfo group.
  • the sulfo group-containing group is preferably a group represented by -L-SO 3 H for the reason that the effect of the present invention is more excellent.
  • L represents a single bond or a divalent organic group.
  • Specific examples and preferred embodiments of the divalent organic group are the same as the carboxy group-containing group described above.
  • the divalent organic group is preferably a divalent aliphatic hydrocarbon group because the effects of the present invention are more excellent.
  • the content of the carboxy group-containing group with respect to the entire surface-modified halloysite in the halloysite of the present invention is not particularly limited. From the reason that the effect of the invention is more excellent, it is preferably 0.1 to 15 mmol / g, more preferably 0.1 to 12 mmol / g, and still more preferably 0.1 to 10 mmol / g. Among these, from the reason that the effect of the present invention is more excellent, it is preferably 0.7 mmol / g or more, and more preferably 1.0 mmol / g or more.
  • the content of the sulfo group-containing group with respect to the entire surface-modified halloysite in the halloysite of the present invention (hereinafter also referred to as “sulfo group content”) is not particularly limited. From the reason that the effect of the invention is more excellent, it is preferably 0.1 to 15 mmol / g, more preferably 0.1 to 12 mmol / g, and still more preferably 0.1 to 10 mmol / g.
  • the halloysite of the present invention preferably further has a hydroxyl group on the surface for the reason that the effect of the present invention is more excellent.
  • a hydroxyl group on the surface for the reason that the effect of the present invention is more excellent.
  • the method for producing the halloysite of the present invention is not particularly limited, but for the reason that the activity of the resulting surface-modified halloysite is more excellent, halloysite (surface-unmodified halloysite) (hereinafter, surface-unmodified halloysite is simply referred to as “halloysite” or “ Hs ”) and a surface modifier described later.
  • a method of reacting a part of the hydroxyl group on the surface of halloysite with a surface modifier is preferable because the activity of the obtained surface modified halloysite is more excellent.
  • a surface-modified halloysite in which a carboxy group-containing group or a sulfo group-containing group and a hydroxyl group coexist uniformly is obtained. More specifically, a method of stirring the halloysite and the surface modifier in a solvent under high temperature (for example, 50 to 200 ° C.) conditions and the like can be mentioned.
  • the solvent is not particularly limited, but is preferably an organic solvent and more preferably toluene because the activity of the resulting surface-modified halloysite is more excellent.
  • the halloysite is surface-modified by the above method. More specifically, a carboxy group-containing group or a sulfo group-containing group is introduced on the surface of the halloysite (for example, when the halloysite is in the shape of a nanotube, alumina on the inner surface).
  • halloysite surface unmodified halloysite
  • examples of other shapes of halloysite include a sheet shape, a spherical shape, an angular nodule shape, and a plate shape.
  • Specific examples and preferred embodiments of the halloysite shape are the same as those of the halloysite of the present invention described above.
  • Halloysite usually has a hydroxyl group (OH group) on its surface.
  • the amount of hydroxyl group (surface hydroxyl group amount) present on the surface of halloysite (surface-unmodified halloysite) is not particularly limited, but is 0.1 to 15 mmol / g for the reason that the activity of the surface-modified halloysite obtained is more excellent. Is preferred.
  • the surface hydroxyl group amount of halloysite is measured by MeLi (methyl lithium) titration (Shimazu et al., Journal of Molecular Catalysis A: Chemical, 182-183, 343-350 (2002)).
  • the quartz content of halloysite is preferably 1.00% by mass or less, more preferably 0.70% by mass or less, and still more preferably 0.40% by mass or less, because the activity of the resulting surface-modified halloysite is more excellent.
  • the lower limit is not particularly limited, but is preferably not detected in the XRD measurement.
  • quartz standard products (JAWE 460 for analysis of free silicic acid in Japan Working Environment Measurement Association) are dispersed in pure water.
  • a sample dispersed in water is collected on a filter which has been previously measured by XRD by suction filtration.
  • the collected sample is dried together with the filter at 105 ° C. for 2 hours and then weighed.
  • the mass of the collected sample is calculated by subtracting the mass of the filter weighed in advance.
  • the peak integrated intensity of quartz is corrected using the peak integrated intensity of the Zn plate (base standard plate) by the base standard absorption correction method.
  • a calibration curve of mass is created from the peak integrated intensity of the quartz standard product, and the quantitative value of quartz in the halloysite powder is calculated using the calibration curve.
  • the quartz content of the halloysite powder is determined.
  • XRD measurement is as follows.
  • -Apparatus used X-ray diffraction analyzer SmartLab (manufactured by Rigaku)
  • ⁇ X-ray tube CuK ⁇ ⁇
  • Optical system Concentration method ⁇ Tube voltage: 45 kV ⁇ Tube current: 200mA
  • Detector One-dimensional semiconductor detector Scan range: 26.0 to 28.0 deg Scan step: 0.01 deg Scan speed: 5 deg / min
  • the halloysite is preferably a purified halloysite (purified halloysite) because the activity of the resulting surface-modified halloysite is more excellent.
  • the degree of purification is appropriately selected from the viewpoint of utilization purpose, performance, manufacturing cost, and the like.
  • the method for purifying halloysite is not particularly limited, but from the viewpoint of removing many coexisting minerals other than halloysite and obtaining a lot of halloysite nanotube particles, a method using wet hydration or centrifugation is preferred.
  • a drying method of the refined halloysite slurry obtained by the above method for example, (1) It is spread and dried on an unglazed plate or a filter cloth.
  • the halloysite is a powder containing granules in which halloysites containing halloysite nanotubes are aggregated for the reason that the activity of the resulting surface-modified halloysite is superior, and the granules originate from the tube holes of the halloysite nanotubes. It is preferably a halloysite powder (hereinafter also referred to as “the halloysite powder of the present invention” or “the powder of the present invention”) having pores and second pores different from the first pores.
  • the halloysite powder of the present invention has the following advantages. ⁇ High bulk specific gravity, low dust generation and easy handling. -Good fluidity, excellent supply and suitable for mass production. That is, while being easy to handle and supply, the presence of the second pores allows the solution to penetrate into the nanotubes constituting the granules, thereby enabling surface modification.
  • the granule contained in the powder of the present invention is a granule in which halloysites containing halloysite nanotubes are aggregated, and pores derived from tube holes of halloysite nanotubes (first It can be confirmed by, for example, a scanning electron microscope (SEM) photograph.
  • SEM scanning electron microscope
  • the fact that the granules of the present invention further have second pores different from the first pores can be confirmed, for example, by an SEM photograph of the granule cross section.
  • the cross section of the granule is exposed, for example, by processing the granule with a focused ion beam (FIB). It can also be confirmed from the pore distribution measurement.
  • FIB focused ion beam
  • the method for producing the halloysite powder of the present invention is not particularly limited, but is a method for producing the halloysite powder of the present invention described above, at least a step of preparing a halloysite slurry containing halloysite nanotubes (slurry preparation step), And a step of preparing a powder from the slurry (powder preparation step).
  • the powder preparation step include a step of obtaining a powder from the slurry prepared in the slurry preparation step (for example, a dispersed phase obtained by centrifugation) by medium fluidized drying or a spray dryer.
  • the means for preparing the powder from the slurry is not limited to the above-described medium fluidized drying and spray drying.
  • the production method of the present invention may further include a step of firing the powder obtained in the powder preparation step (firing step).
  • the surface modifier is not particularly limited as long as it is a compound capable of introducing a carboxy group-containing group or a sulfo group-containing group on the surface of halloysite.
  • a compound capable of introducing a carboxy group-containing group to the surface of halloysite is not particularly limited, but it is energy-saving and efficient (reaction of the surface of halloysite).
  • Carboxylic acid, carboxylate and carboxylic acid for the reason that the activity of the resulting surface-modified halloysite is more excellent). It is preferably at least one compound selected from the group consisting of anhydrides.
  • the carboxy group-containing group-introduced surface modifier is preferably a carboxylic acid anhydride because the activity of the resulting surface-modified halloysite is more excellent.
  • carboxylic acid anhydride examples include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 4-methyl Examples include hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, phthalic anhydride, diglycolic anhydride, and glutaric anhydride.
  • diglycolic acid anhydride is preferred because it reacts with the OH group on the surface of the halloysite to bond one to O and the other forms a carboxylic acid group, and the resulting surface-modified halloysite is more excellent in activity.
  • the addition amount of the carboxy group-containing group-introducing surface modifier to the halloysite is preferably 1 to 1000 equivalents relative to the surface hydroxyl group amount of the halloysite, because the activity of the resulting surface-modified halloysite is more excellent. It is more preferable that the amount is equal.
  • the addition amount of the carboxy group-containing group-introducing surface modifier to halloysite is 1 to 1000 mmol for 1 g of halloysite (surface-unmodified halloysite) because the resulting surface-modified halloysite activity is more excellent. It is preferably 1 to 200 mmol, more preferably 1 to 100 mmol.
  • the substitution rate of Hs-COOH is not particularly limited, but is preferably 1 to 99 mol%, more preferably 10 to 90 mol%, and more preferably 20 to 80 mol%, because the activity of the surface-modified halloysite obtained is more excellent. More preferably, it is particularly preferably 30 to 80 mol%.
  • the substitution rate of Hs—COOH means that in Hs—COOH obtained by reacting a part of the hydroxyl group on the surface of halloysite (surface unmodified halloysite) with a surface modifier, the halloysite (surface unmodified). This refers to the ratio of the carboxy group content (mmol / g) of Hs—COOH to the surface hydroxyl group content (mmol / g) of halloysite.
  • the compound capable of introducing a sulfo group-containing group to the surface of halloysite (hereinafter also referred to as “sulfo group-containing group-introducing surface modifier”) is not particularly limited, but because the activity of the resulting surface-modified halloysite is more excellent It is preferably at least one compound selected from the group consisting of sulfonic acid, sulfonic acid salt and sulfonic acid ester.
  • the sulfo group-containing group-introduced surface modifier reacts efficiently and efficiently (reacts with the OH group on the surface of halloysite in one step to produce a sulfo group-containing group in which one is bonded to Al—O).
  • a sulfonic acid ester is preferable, and a cyclic sulfonic acid ester is more preferable.
  • the cyclic sulfonate ester include 1,3-propane sultone, 1,2-propane sultone, 1,4-butane sultone, 1,2-butane sultone, 1,3-butane sultone, 2,4-butane sultone, and 1,3 -Pentanthruton and the like. Of these, 1,3-propane sultone is preferred because the activity of the resulting surface-modified halloysite is superior.
  • the addition amount of the sulfo group-containing group-introducing surface modifier to the halloysite is preferably 1 to 1000 equivalents relative to the surface hydroxyl group amount of the halloysite, because the activity of the resulting surface modified halloysite is more excellent. It is more preferable that the amount is equal.
  • the addition amount of the sulfo group-containing group-introducing surface modifier to halloysite is 1 to 1000 mmol for 1 g of halloysite (surface unmodified halloysite) because the resulting surface-modified halloysite activity is more excellent. It is preferably 1 to 200 mmol, more preferably 1 to 100 mmol.
  • the substitution rate of Hs-PS is not particularly limited, it is preferably 1 to 99 mol%, more preferably 10 to 90 mol%, and more preferably 20 to 80 mol%, because the activity of the resulting surface-modified halloysite is more excellent. More preferably, it is particularly preferably 30 to 80 mol%.
  • the substitution rate of Hs-PS refers to the halloysite (surface unmodified) in Hs-PS obtained by reacting a part of the hydroxyl group on the surface of halloysite (surface unmodified halloysite) with a surface modifier. The ratio of the sulfo group content (mmol / g) of Hs-PS to the surface hydroxyl group content (mmol / g) of halloysite.
  • the catalytic reaction of the present invention is a catalytic reaction using the above-described halloysite of the present invention as a solid catalyst.
  • the halloysite of the present invention has a structure in which a carboxy group-containing group or a sulfo group-containing group is bonded to the surface of a halloysite having a fine structure (for example, in the form of a nanotube or the like). It is extremely useful for acid-catalyzed reactions).
  • the halloysite of the present invention is a hyrosite having a carboxy group-containing group on the surface, it is extremely useful in a method for synthesizing a monosaccharide by hydrolyzing a polysaccharide (including oligosaccharides such as disaccharides). . Further, when the halloysite of the present invention is a hyrosite having a sulfo group-containing group on the surface, it is useful for dehydrating and decomposing sugars. Useful.
  • the solvent used for the catalytic reaction is not particularly limited, but for reasons of improving the yield, an organic solvent is preferable, and an alcohol (particularly, More preferably an alcohol having 3 or more carbon atoms, particularly preferably an alcohol having 4 or more carbon atoms (butanol (for example, 2-butanol)).
  • reaction time of the catalytic reaction of the present invention is not particularly limited, it is preferably 1 hour or longer, more preferably 3 hours or longer, and even more preferably 10 hours or longer, for the reason of improving the yield.
  • the upper limit is not particularly limited, but is preferably 100 hours or less.
  • Purified halloysite (purified halloysite 1 and 2) was prepared as follows. In addition, it was confirmed from the SEM photograph that the refined halloysites 1 and 2 correspond to the powder of the present invention described above.
  • ⁇ Purified halloysite 1> The clay component (Iitoyo clay) generated at the Iwatani factory of JFE Mineral Co., Ltd. Iidayo Mining Co., Ltd. This clay component contains fine sand (quartz) represented by halloysite and SiO 2 as main components.
  • Iitoyo clay and water were put into a high-speed mixer to obtain a slurry in which Iitoyo clay was dispersed in water.
  • the slurry was passed through a sieve having an opening of 45 ⁇ m to remove coarse particles of +45 ⁇ m on the mesh. Under-net-45 ⁇ m slurry was suction filtered and the residue on the filter was recovered as a dehydrated cake.
  • the dehydrated cake and water were added to a high-speed mixer, and an anionic polymer surfactant was added as a dispersant to obtain a dispersion slurry.
  • the obtained dispersed slurry was separated into a sedimented phase and a dispersed phase with a centrifugal force of 2470 G using a centrifuge. And the dispersed phase was collect
  • the obtained purified halloysite is designated as purified halloysite 1.
  • the obtained purified halloysite 1 contained nanotube-shaped halloysite (halloysite nanotube).
  • the obtained purified halloysite 1 had a hydroxyl group on the surface. It was 3.55 mmol / g when the amount of surface hydroxyl groups of halloysite was measured.
  • the method for measuring the surface hydroxyl group content of halloysite is as described above.
  • Purified halloysite was prepared according to the same procedure as purified halloysite 1 except that drying was performed using a spray dryer instead of the medium fluidized dryer.
  • the obtained purified halloysite is designated as purified halloysite 2.
  • the resulting purified halloysite 2 contained nanotube-shaped halloysite (halloysite nanotube).
  • the obtained purified halloysite 2 had a hydroxyl group on the surface. It was 3.55 mmol / g when the amount of surface hydroxyl groups of halloysite was measured.
  • the method for measuring the surface hydroxyl group content of halloysite is as described above.
  • the XRD pattern of the halloysite (the halloysite before surface modification) used in the Example is shown.
  • (A) is the XRD pattern of the purified halloysite 1 described above
  • (B) is the XRD pattern of the halloysite manufactured by SIGMA-ALDRICH described above.
  • Purified halloysite 2 showed the same XRD pattern as purified halloysite 1.
  • Gibbsite and quartz peaks appeared in the XRD pattern of SIGMA-ALDRICH's halloysite (B), whereas no gibbsite was detected in the XRD patterns of purified halloysite 1 and 2 (A). The peak of was also very low. Therefore, it can be said that the refined halloysites 1 and 2 are high in purity with few impurities such as gibbsite and quartz.
  • the quartz content of the purified halloysite 1 and 2 and the halloysite manufactured by SIGMA-ALDRICH was measured, the quartz content of the purified halloysite 1 and 2 was 0.3% by mass, and the quartz content of the halloysite manufactured by SIGMA-ALDRICH was included. The amount was 1.2% by mass.
  • Example 1-1 The obtained purified halloysite 1 was dried at 150 ° C. for 1 hour. 40 mL of anhydrous toluene and 1.27 mmol of diglycolic anhydride (1,4-dioxane-2,6-dione) (the following structural formula) were added to purified dried halloysite 1 (0.20 g) (the surface hydroxyl group of halloysite) 1.8 equivalent to the amount), 0.25 mmol of N, N-dimethyl-4-aminopyridine (DMAP) (catalytic amount) and 2.5 mmol of triethylamine (NEt 3 ) (base) were added, and sonication was performed. For 1 hour, and then stirred at reflux (70 ° C., 72 hours). Subsequently, the purified halloysite 1 was surface-modified by washing with distilled water after filtration and performing a drying treatment.
  • DMAP N-dimethyl-4-aminopyridine
  • NEt 3 trieth
  • the halloysite after the surface modification is a halloysite (surface modified halloysite) having a carboxy group-containing group (—COCH 2 OCH 2 —COOH) on the inner surface of the halloysite nanotube. It was.
  • the carboxy group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the carboxy group content was estimated to be 0.6 mmol / g.
  • Example 1-2 The addition amount of diglycolic anhydride is 1.90 mmol, the addition amount of N, N-dimethyl-4-aminopyridine (DMAP) is 0.37 mmol, and the addition amount of triethylamine (NEt 3 ) (base) is 3.
  • DMAP N, N-dimethyl-4-aminopyridine
  • NEt 3 triethylamine
  • Purified halloysite 1 was surface-modified according to the same procedure as in Example 1-1 except that the amount was 7 mmol.
  • the halloysite after the surface modification is a halloysite (surface modified halloysite) having a carboxy group-containing group (—COCH 2 OCH 2 —COOH) on the inner surface of the halloysite nanotube. It was.
  • the carboxy group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the carboxy group content was estimated to be 0.9 mmol / g.
  • Example 1-3 The added amount of diglycolic anhydride is 2.53 mmol, the added amount of N, N-dimethyl-4-aminopyridine (DMAP) is 0.5 mmol, and the added amount of triethylamine (NEt 3 ) (base) is 5.
  • DMAP N, N-dimethyl-4-aminopyridine
  • NEt 3 triethylamine
  • Purified halloysite 1 was surface-modified according to the same procedure as in Example 1-1 except that the amount was 0 mmol.
  • the halloysite after the surface modification is a halloysite (surface modified halloysite) having a carboxy group-containing group (—COCH 2 OCH 2 —COOH) on the inner surface of the halloysite nanotube. It was.
  • the carboxy group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the carboxy group content was estimated to be 2.8 mmol / g.
  • “Halloysite” is an FT-IR (Fourier Transform Infrared Spectroscopy) spectrum before surface modification (purified halloysite 1), and “Hs-COOH (0.6)” is after surface modification (Example 1).
  • “Hs-COOH (0.9)” is the FT-IR spectrum after surface modification (Example 1-2)
  • “Hs-COOH (2.8)” Is the FT-IR spectrum after surface modification (Example 1-3).
  • Example 1-1 was used except that instead of the purified halloysite 1, the above-mentioned halloysite (containing nanotube-shaped halloysite (halloysite nanotube)) (surface hydroxyl group amount: 2.5 mmol / g) manufactured by SIGMA-ALDRICH was used. The halloysite was surface modified according to a similar procedure.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a carboxyl group-containing group (—COCH 2 OCH 2 —COOH) on the inner surface of the halloysite nanotube.
  • the carboxy group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the obtained surface-modified halloysite was subjected to TG-DTA (Thermogravimetry-Differential Thermal Analysis) measurement, and the carboxy group content was estimated to be 0.3 mmol / g.
  • TG-DTA Thermogravimetry-Differential Thermal Analysis
  • Example 1-6 The obtained refined halloysite 1 was dried at 150 ° C. for 1 hour, and then pulverized until the shape of the nanotube disappeared, whereby a refined halloysite 1 crushed product containing no nanotube-shaped halloysite (purified halloysite 1 crushed product) was obtained. Obtained. Then, the purified halloysite 1 pulverized product was surface-modified according to the same procedure as in Example 1-1 except that the purified halloysite 1 pulverized product was used in place of the purified halloysite 1.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a carboxy group-containing group (—COCH 2 OCH 2 —COOH) on the surface of the halloysite.
  • the carboxy group-containing group is bonded to alumina on the surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the carboxy group content was estimated to be 0.6 mmol / g.
  • Example 1-7 Purified halloysite 2 was surface-modified according to the same procedure as in Example 1-1, except that purified halloysite 2 was used instead of purified halloysite 1.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a carboxyl group-containing group (—COCH 2 OCH 2 —COOH) on the inner surface of the halloysite nanotube.
  • the carboxy group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—COCH 2 OCH 2 —COOH.
  • the carboxy group content was estimated to be 0.6 mmol / g.
  • the table-modified halloysites of Examples 1-1 to 1-4 and Examples 1-6 to 1-7 were halloysites having a hydroxyl group on the surface.
  • the FT-IR spectra of the surface modified halloysites of Examples 1-1 to 1-3 and Examples 1-6 to 1-7 no interaction between carboxy group-containing groups was observed.
  • carboxy group-containing groups and hydroxyl groups coexist uniformly on the surface.
  • Example 2-1> The obtained purified halloysite 1 was dried at 150 ° C. for 1 hour. 10 mL of anhydrous toluene and 25 mmol of 1,3-propane sultone (35.2 equivalents relative to the surface hydroxyl amount of halloysite) were added to the dried purified halloysite 1 (0.20 g), and sonication was performed for 1 hour. Thereafter, the mixture was stirred while refluxing (120 ° C., 72 hours). Subsequently, the purified halloysite 1 was surface-modified by washing with distilled water after filtration and performing a drying treatment.
  • FIG. 3 shows FT-IR (Fourier Transform Infrared Spectroscopy) spectra of halloysite before and after surface modification.
  • A is the spectrum before surface modification
  • b is the spectrum after surface modification.
  • the obtained halloysite was a halloysite (surface-modified halloysite) having a sulfo group-containing group (—C 3 H 6 —SO 3 H) on the inner surface of the halloysite nanotube.
  • the sulfo group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—C 3 H 6 —SO 3 H.
  • the sulfo group content was estimated to be 1.4 mmol / g.
  • Example 2-2 Example 2-1, except that the above-described halloysite (containing nanotube-shaped halloysite (halloysite nanotube)) (surface hydroxyl group content: 2.5 mmol / g) manufactured by SIGMA-ALDRICH was used in place of the purified halloysite 1
  • the halloysite was surface modified according to a similar procedure.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a sulfo group-containing group (—C 3 H 6 —SO 3 H) on the inner surface of the halloysite nanotube.
  • the sulfo group-containing group is bonded to alumina on the inner surface of the halloysite nanotube to form a structure represented by Al—O—C 3 H 6 —SO 3 H.
  • the sulfo group content was estimated to be 0.7 mmol / g.
  • Example 2-7 The purified halloysite 1 pulverized product was surface-modified according to the same procedure as in Example 2-1, except that the purified halloysite 1 pulverized product described above was used instead of the purified halloysite 1.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a sulfo group-containing group (—C 3 H 6 —SO 3 H) on the surface of the halloysite.
  • the sulfo group-containing group is bonded to alumina on the surface of halloysite to form a structure represented by Al—O—C 3 H 6 —SO 3 H.
  • the sulfo group content was estimated to be 1.4 mmol / g.
  • Example 2-8 Purified halloysite 2 was surface-modified according to the same procedure as in Example 2-1, except that purified halloysite 2 was used instead of purified halloysite 1.
  • the halloysite after the surface modification was a halloysite (surface-modified halloysite) having a sulfo group-containing group (—C 3 H 6 —SO 3 H) on the inner surface of the halloysite nanotube.
  • the sulfo group-containing group is bonded to alumina on the surface of halloysite to form a structure represented by Al—O—C 3 H 6 —SO 3 H.
  • the sulfo group content was estimated to be 1.4 mmol / g.
  • the surface-modified halloysites of Examples 2-1, 2-2, 2-7, and 2-8 were halloysites having a hydroxyl group on the surface.
  • Hs—COOH represents surface-modified halloysite (Hs—COOH)
  • Hs represents halloysite (surface-unmodified halloysite).
  • carboxy group content represents the carboxy group content described above.
  • substitution rate represents the above-described substitution rate.
  • Reaction time represents the time during which cellobiose was hydrolyzed.
  • Examples 1-1 to 1-3 and 1-7 produced using the purified halloysite corresponding to the powder of the present invention described above showed higher catalytic activity.
  • the halloysite manufactured by SIGMA-ALDRICH used in Example 1-4 contains a large amount of impurities (quartz and gibbsite), whereas the purification used in Examples 1-1 to 1-3 and 1-7. Since halloysite has few impurities (FIG. 2), it is considered that it showed higher catalytic activity.
  • the comparison between Example 1-1 and Example 1-7 having a carboxy group content of 0.6 mmol / g was obtained by spray drying. Examples 1-7 using purified halloysite showed higher catalytic activity.
  • Example 1-1 to 1-3 comparative of modes using purified halloysite obtained by medium fluidized drying
  • Example 1-2 having a carboxy group content of 0.7 mmol / g or more.
  • 1-3 showed higher catalytic activity.
  • Example 1-3 having a carboxy group content of 1.0 mmol / g or more showed higher catalytic activity.
  • the surface-modified halloysite of Example 1-3 was used as a solid catalyst and xylan, a polysaccharide, was hydrolyzed, xylose was obtained in a high yield (89.3%).
  • Example 1-5 in which the reaction time is 10 hours or more showed a higher yield.
  • Example 2-1 20 mg of the surface-modified halloysite of Example 2-1 and 40 mg of fructose and 2 mL of the solvent described in Table 2 below were added to the reaction vessel and stirred, and dehydration decomposition of fructose was performed using the surface-modified halloysite as a solid catalyst ( (120 ° C., 2 hours) (Examples 2-3 to 2-5). Also, fructose was dehydrated and decomposed according to the same procedure as in Example 2-1 except that the dehydrating decomposition time was changed to 4 hours (Example 2-6). Further, fructose was dehydrated and decomposed according to the same procedure as in Example 2-3 except that no surface-modified halloysite was added (Comparative Example 2-1).
  • fructose was dehydrated and decomposed according to the same procedure as in Example 2-3 except that the above-described purified halloysite 1 (non-surface-modified) was used instead of the surface-modified halloysite (Comparative Example 2- 2). Further, fructose was dehydrated and decomposed according to the same procedure as in Example 2-6 except that the surface-modified halloysite was not added (Comparative Example 2-3). Further, fructose was dehydrated and decomposed according to the same procedure as in Example 2-6, except that the above-described purified halloysite 1 (non-surface-modified) was used instead of the surface-modified halloysite (Comparative Example 2- 4). Table 2 below shows the reaction conversion rate and yield (the yield of the target substance, hydroxymethylfurfural (HMF)). The reaction conversion rate and yield were determined from HPLC (High Performance Liquid Chromatography).
  • Hs-PS represents surface-modified halloysite (Hs-PS)
  • Hs represents halloysite (surface-unmodified halloysite).
  • the “sulfo group content” represents the above-described sulfo group content.
  • Substitution rate represents the above-described substitution rate.
  • Reaction time represents the time during which dehydration decomposition of fructose was performed.
  • Examples 2-1 and 2-8 produced using the purified halloysite corresponding to the powder of the present invention described above showed higher catalytic activity.
  • the halloysite manufactured by SIGMA-ALDRICH used in Example 2-2 contains many impurities (quartz and gibbsite), whereas the purified halloysite used in Examples 2-1 and 2-8 contains impurities. Since it is small (FIG. 2), it is thought that the higher catalyst activity was shown.
  • Example 1-7 using purified halloysite obtained by spray drying showed higher catalytic activity.
  • Examples 2-3 and 2-4 using an alcohol having 3 or more carbon atoms as a reaction solvent are: A higher yield was shown. Among them, Example 2-3 using an alcohol having 4 or more carbon atoms as a reaction solvent showed a higher yield.
  • Examples 2-1 and 2-3 and 2-6 the comparison between the aspects in which only the reaction time is different
  • Examples 2-1 and 2-6 in which the reaction time is 3 hours or more are: A higher yield was shown.
  • Example 2-1 having a reaction time of 10 hours or more showed a higher yield. It is considered that the fructose dimer produced as an intermediate was converted to HMF by extending the reaction time.

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Abstract

L'objectif de la présente invention est de fournir un nouveau catalyseur solide ayant une activité catalytique élevée, un procédé de production du catalyseur solide, et une réaction catalytique utilisant le catalyseur solide. Une halloysite à surface modifiée selon la présente invention est une halloysite ayant un groupe contenant un groupe carboxy ou un groupe contenant un groupe sulfo sur sa surface.
PCT/JP2017/038513 2016-10-25 2017-10-25 Halloysite à surface modifiée, procédé de production d'halloysite à surface modifiée et réaction catalytique Ceased WO2018079605A1 (fr)

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US16/344,955 US11932544B2 (en) 2016-10-25 2017-10-25 Surface-modified halloysite, method for producing surface-modified halloysite, and catalytic reaction
CN201780065612.0A CN109890755B (zh) 2016-10-25 2017-10-25 表面修饰埃洛石、表面修饰埃洛石的制造方法和催化反应
KR1020197011881A KR102227904B1 (ko) 2016-10-25 2017-10-25 표면 수식 할로이사이트, 표면 수식 할로이사이트의 제조 방법, 및 촉매 반응
JP2018547722A JP7104630B2 (ja) 2016-10-25 2017-10-25 表面修飾ハロイサイト、表面修飾ハロイサイトの製造方法、及び、触媒反応
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KR102420119B1 (ko) * 2021-11-19 2022-07-13 대한기술연구원 주식회사 고습윤 환경에 노출된 수처리 콘크리트 구조물의 타일 시공방법

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